CN108899566A - A kind of tertiary amine groups amphoteric ion exchange membrane and preparation method thereof - Google Patents
A kind of tertiary amine groups amphoteric ion exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of membrane, a kind of tertiary amine groups amphoteric ion exchange membrane and preparation method thereof is provided.There is tertiary amine group and sulfonic acid group simultaneously in membrane material.The invention has the advantages that preparing amphoteric ion exchange membrane as basic group and sulfonic acid group using uncharged tertiary amine group, tertiary amine group can form " acid-base pair " effect with sulfonic acid group, to effectively improve the resistance vanadium performance of film, and promote the conduction of proton, make film ionic conductivity and ion selectivity with higher simultaneously, while introducing the stability that tertiary amine group substantially increases film.
Description
Technical field
The invention belongs to technical field of membrane, it is related to a kind of amphoteric ion exchange membrane and preparation method thereof, is related specifically to
A kind of preparation method of tertiary amine groups amphoteric ion exchange membrane.
Background technique
With the aggravation of environmental pollution and energy crisis, the development and utilization of the renewable new energies such as solar energy, wind energy are more next
More it is valued by people.In order to improve the economy and stability of these renewable energy, there is an urgent need to a kind of efficient by people
The extensive energy storage technology of rate, high reliability.The long service life that all-vanadium flow battery (VRBs) has by it, can depth charge and discharge
Electricity, fast response time, flexible design, it is pollution-free the features such as and become New Energy Industry research focus.
Critical component of the amberplex as battery, plays an important role in VRBs.It should separate yin-yang two
Pole, the ion channel for preventing vanadium ion Cross slot interference from providing connection again have emphatically the performance of VRBs to form cell circuit
The influence wanted.Ideal VRBs amberplex requires ionic conductivity high, and ion selectivity is high, and chemical stability is good, cost
The features such as low.
Most common amberplex is proton ion exchange membrane (PEM), PEM although proton conductivity with higher,
But its vanadium ion permeability is larger.Corresponding anion-exchange membrane (AEM) is because having positively charged group that can repel vanadium
Ion has preferable resistance vanadium, but its surface resistance is larger.Recently, amphoteric ion exchange membrane receives extensive research.It was both
The advantages of there is negative electricity group again with positive charged group, two kinds of amberplexes can be combined well, at the same it is with higher
Ionic conductivity and ion selectivity.
Currently, amphoteric ion exchange membrane is mostly used the ion-exchange group with positive charge such as quaternary amine as basic group, adopt
Also fewer with groups such as uncharged tertiary amines, tertiary amine can protonate under acidic environment, so that the lotus that becomes positively charged, plays
The effect of vanadium is hindered, and " acid-base pair " effect can be formed by hydrogen bond and sulfonate radical, promotes proton conduction, and be effectively improved film
Chemical stability.
Summary of the invention
The present invention is directed to improve the ionic conductivity of amberplex used for all-vanadium redox flow battery, ion selectivity and chemistry
Stability provides a kind of amphoteric ion exchange membrane and preparation method thereof simultaneously containing sulfonic acid group and tertiary amine group；Pass through
It is acylated and tertiary amine is introduced into polyphenylene ether polymer and prepares tertiary-aminated polyphenylene oxide (PPO-TA) by tertiary amino functional reaction, and will
Made PPO-TA and sulfonated polyether-ether-ketone (SPEEK) use direct blending, are prepared for ion choosing a kind of while with higher
The new type amphoteric amberplex of selecting property, ionic conductivity and stability.
Technical solution of the present invention：
A kind of tertiary amine groups amphoteric ion exchange membrane is tertiary-aminated polyphenylene oxide (PPO-TA) and sulfonated polyether-ether-ketone (SPEEK)
Polymer, structure are：
SPEEK
PPO-TA
Tertiary amine group contained in tertiary amine groups amphoteric ion exchange membrane has the ability for receiving proton, as proton acceptor；
Proton acceptor forms " acid-base pair " structure with the sulfonic acid group as proton donor, and " acid-base pair " structure is connected by hydrogen bond, had
Effective resistance vanadium and the ability for promoting proton conduction.
A kind of preparation method of tertiary amine groups amphoteric ion exchange membrane, synthetic route are as follows：
Specific step is as follows：
(1) under the conditions of ice-water bath, polyether-ether-ketone (PEEK) is dissolved in the concentrated sulfuric acid, is vigorously stirred；Work as polymer
After being completely dissolved, reaction temperature is increased to 40 DEG C -80 DEG C, reaction a period of time；To after the reaction was completed, reaction solution be poured into stirring
In the ice water of state, it is sulfonated polyether-ether-ketone (SPEEK) polymer that precipitating, which is precipitated,；The product is cleaned repeatedly with deionized water,
Until pH value reaches neutral, then it is completely dried under vacuum conditions；
(2) under stirring, PPO is dissolved in methylene chloride, PPO solution is made；Under nitrogen protection, to dichloromethane
Aluminum trichloride (anhydrous) is added in alkane and is vigorously stirred, under the conditions of ice-water bath, is slowly added to certain proportion 4- fluorobenzoyl chloride, obtains
To mixed solution；PPO solution is then added in mixed solution, 8h or more is reacted at 50 DEG C -80 DEG C；After the reaction was completed, will
Reaction solution pours into a large amount of ethyl alcohol, and it is to be acylated PPO polymer that precipitating, which is precipitated,；Polymer is washed repeatedly with water and ethyl alcohol,
Vacuum drying；
(3) the acylation PPO polymer for taking step (2) to synthesize is dissolved in dimethyl acetamide (DMAC), is then added one
The 2 of certainty ratio, 4,6- tri- (dimethylamino methyl) phenol and excessive cesium carbonate react 8h or more at 80 DEG C -120 DEG C；?
In reaction process, nitrogen is bubbled in the solution, in favor of the removal of water；After reaction, reaction solution is poured into a large amount of methanol,
The tertiary amino functional PPO (PPO-TA) for being precipitated finally.Then water and the thorough wash products of methanol are used, are dried in vacuo；
(4) PPO-TA of the SPEEK that (1) synthesizes the step of different proportion and step (2) synthesis is taken to be dissolved in casting film agent respectively
In, the casting solution for being 20g/L-50g/L at concentration；Casting solution is added dropwise on casting film glass plate, and sufficiently drying in an oven,
The tertiary amine groups amphoteric ion exchange membrane with a thickness of 30 μm -70 μm is made；A small amount of water is added in tertiary amine groups amphoteric ion exchange membrane,
And it is gently removed from casting film glass plate；At room temperature, by prepared tertiary amine groups amphoteric ion exchange membrane be immersed in from
12h is in sub- water to remove impurity；Then, it is immersed in 12h in acid, it is made to carry out sufficient ion exchange；Later again by it
It impregnates in deionized water, removes extra acid.
The casting film agent is dimethylformamide (DMF), dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO), N
The mixed solvent of methyl pyrrolidone (NMP) wherein one or more, dry film temperature be 40 DEG C -70 DEG C, dry the film time be
15h-36h。
What the degree of substitution foundation of the acylation PPO and tertiary amino functional PPO that synthesize in the step (2) and (3) were added
Depending on the ratio of 4- fluorobenzoyl chloride and 2,4,6- tri- (dimethylamino methyl) phenol and PPO, 100% is reached as high as.
The amphoteric ion exchange membrane of different mixture ratio is made in the step (4) according to SPEEK with PPO-TA ratio difference
SPEEK/PPO-TA (X%), X are mass ratio, up to 100% shared by PPO-TA in film.
The invention has the advantages that design is simultaneously using SPEEK and PPO-TA respectively as acid and alkaline polymer
It is prepared for a kind of tertiary amine groups amphoteric ion exchange membrane applied to vanadium flow battery.Two are prepared using tertiary amine group as basic group
Property amberplex, tertiary amine group can with sulfonic acid group formed soda acid pairing effect, both can effectively improve film resistance vanadium performance, together
When can promote the conduction of proton, make film ionic conductivity and ion selectivity with higher simultaneously, also improve simultaneously
The stability of film.Prepared tertiary amine groups amphoteric ion exchange membrane can express very excellent battery performance in this way,
Energy efficiency is much better than Nafion212, the common sulfonate film such as SPEEK, and has very good stability, circulating battery 200
The behind efficiency of circle has no obvious decaying, and the mass loss after impregnating 45 days in high price vanadium ion solution is far below sulfonated polyether ether
Ketone film.
Specific embodiment
The present invention is described in further detail below by specific example.
Embodiments described below is only a part of the invention, not all embodiment.Embodiment is listed
Amphoteric ion exchange membrane preparation process and performance characterization without aromatic yl ether key, these embodiments only say the present invention
It is bright, do not belong to the scope of protection of the present invention within.
Embodiment 1
Under the conditions of ice-water bath, by 5g polyether-ether-ketone (PEEK) in being dissolved in the 100ml concentrated sulfuric acid, it is vigorously stirred.When
After polymer is completely dissolved, reaction temperature is increased to 50 DEG C, reacts 7h.To after the reaction was completed, reaction solution be poured into stirring
Ice water in, be precipitated be precipitated as sulfonation degree be 78% sulfonated polyether-ether-ketone (SPEEK) polymer.Product be washed with deionized water to
Neutrality is completely dried under vacuum environment；
It takes SPEEK synthesized by 0.15g to be dissolved in 4mlDMF, casts at 50 DEG C and form a film for 24 hours.At room temperature, film is impregnated
12h is in deionized water to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again will
Film impregnates in deionized water, removes extra acid.SPEEK film is made, which is 46.1%, surface resistance 0.371
Ω cm2, vanadium ion permeability are 1.18 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 87.84%, VE 91.57%, EE 80.44%.In 1.5M VO2 +/3M H2SO445 are impregnated in solution
Mass loss after it is 18.4%.
Embodiment 2
3g PPO is dissolved in 25ml methylene chloride under stirring, PPO solution is made, then burnt at another three mouthfuls
25ml methylene chloride is added in bottle, 2.4g aluminum trichloride (anhydrous) is added under nitrogen protection and is vigorously stirred, in ice-water bath condition
Under be slowly added to 1.83ml 4- fluorobenzoyl chloride.The PPO solution prepared before being then added in this mixed solution, at 60 DEG C
Lower reaction 10h.Reaction solution is poured into a large amount of ethyl alcohol after the reaction was completed, is precipitated and is precipitated as the acylation PPO that degree of substitution is 50%
Polymer.Polymer is washed repeatedly with water and ethyl alcohol, vacuum drying；
It takes the 1g of above-mentioned synthesis to be acylated PPO to be dissolved in 30ml dimethyl acetamide (DMAC), 1g 2,4,6- is then added
Three (dimethylamino methyl) phenol and 1.6g cesium carbonate, react 10h at 110 DEG C.During the reaction, nitrogen rouses in the solution
Bubble, in favor of the removal of water.After reaction, reaction solution is poured into a large amount of methanol, be precipitated degree of substitution be 50% tertiary amine
Functionalization PPO (PPO-TA).Then water and the thorough wash products of methanol, vacuum drying are used.
It takes the PPO-TA of the above-mentioned synthesis of 0.15g to be dissolved in 4mlDMF, casts at 50 DEG C and form a film for 24 hours.At room temperature, by film
Impregnate in deionized water 12h to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.
Film is impregnated in deionized water again, removes extra acid.PPO-TA film is made, which is 21.1%, and surface resistance is
0.583 Ω cm2, vanadium ion permeability are 0.16 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mA
cm-2When current density, CE 97.84%, VE 88.65%, EE 86.74%.In 1.5M VO2 +/3M H2SO4It is soaked in solution
Mass loss of the bubble after 45 days is 2.1%.
Embodiment 3
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.1425gSPEEK and
0.0075g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated in deionized water
12h is to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again by film be immersed in from
In sub- water, extra acid is removed.SPEEK/PPO-TA (5%) film is made, which is 41.8%, surface resistance 0.354
Ω cm2, vanadium ion permeability are 0.82 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 90.04%, VE 91.27%, EE 82.18%.In 1.5M VO2 +/3M H2SO445 are impregnated in solution
Mass loss after it is 14%.
Embodiment 4
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.135gSPEEK and
0.015g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated in deionized water
12h is to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again by film be immersed in from
In sub- water, extra acid is removed.SPEEK/PPO-TA (10%) film is made, which is 37.7%, surface resistance 0.376
Ω cm2, vanadium ion permeability are 0.53 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 95.58%, VE 91.82%, EE 88.01%.In 1.5M VO2 +/3M H2SO445 are impregnated in solution
Mass loss after it is 7.14%.
Embodiment 5
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.1275gSPEEK and
0.0225g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated in deionized water
12h is to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again by film be immersed in from
In sub- water, extra acid is removed.SPEEK/PPO-TA (15%) film is made, which is 33.1%, surface resistance 0.389
Ω cm2, vanadium ion permeability are 0.34 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 97.03%, VE 91.32%, EE 88.6%.In 1.5M VO2 +/3M H2SO4It is impregnated 45 days in solution
Mass loss afterwards is 4.44%.
Embodiment 6
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.12gSPEEK and
0.03g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated into 12h in deionized water
To remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Film is immersed in deionized water again
In, remove extra acid.SPEEK/PPO-TA (20%) film is made, which is 31.1%, and surface resistance is 0.399 Ω
Cm2, vanadium ion permeability are 0.66 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electric current
When density, CE 93.98%, VE 90.76%, EE 85.3%.In 1.5M VO2 +/3M H2SO4After being impregnated 45 days in solution
Mass loss be 3.61%.
Embodiment 7
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.105gSPEEK and
0.045g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated in deionized water
12h is to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again by film be immersed in from
In sub- water, extra acid is removed.SPEEK/PPO-TA (30%) film is made, which is 29.2%, surface resistance 0.439
Ω cm2, vanadium ion permeability are 0.68 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 94.05%, VE 90.01%, EE 84.65%.In 1.5M VO2 +/3M H2SO445 are impregnated in solution
Mass loss after it is 3.42%.
Embodiment 8
The preparation of trunk polymer SPEEK and PPO-TA with described in example 1 and example 2, take respectively 0.075gSPEEK and
0.075g PPO-TA is dissolved in 4mlDMF, is cast at 50 DEG C and is formed a film for 24 hours.At room temperature, film is impregnated in deionized water
12h is to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.Again by film be immersed in from
In sub- water, extra acid is removed.SPEEK/PPO-TA (50%) film is made, which is 26.1%, surface resistance 0.498
Ω cm2, vanadium ion permeability are 0.48 × 10-8cm2s-1, in the test of all-vanadium flow battery monocell, in 80mAcm-2Electricity
When current density, CE 96.42%, VE 89.84%, EE 86.62%.In 1.5M VO2 +/3M H2SO445 are impregnated in solution
Mass loss after it is 2.96%.
Embodiment 9
The preparation of trunk polymer SPEEK is the same as described in example 1.
3g PPO is dissolved in 25ml methylene chloride under stirring, PPO solution is made, then burnt at another three mouthfuls
25ml methylene chloride is added in bottle, 2.4g aluminum trichloride (anhydrous) is added under nitrogen protection and is vigorously stirred, in ice-water bath condition
Under be slowly added to 2.56ml 4- fluorobenzoyl chloride.The PPO solution prepared before being then added in this mixed solution, at 60 DEG C
Lower reaction 10h.Reaction solution is poured into a large amount of ethyl alcohol after the reaction was completed, is precipitated and is precipitated as the acylation PPO that degree of substitution is 70%
Polymer.Polymer is washed repeatedly with water and ethyl alcohol, vacuum drying；
It takes the 1g of above-mentioned synthesis to be acylated PPO to be dissolved in 30ml dimethyl acetamide (DMAC), 1.4g 2,4 is then added,
(dimethylamino methyl) phenol of 6- tri- and 1.6g cesium carbonate, react 10h at 110 DEG C.During the reaction, nitrogen is in the solution
It is bubbled, in favor of the removal of water.After reaction, reaction solution is poured into a large amount of methanol, be precipitated degree of substitution be 70% uncle
Amino-functionalization PPO (PPO-TA).Then water and the thorough wash products of methanol, vacuum drying are used.
It takes 0.135g SPEEK and 0.015g PPO-TA to be dissolved in 4mlDMF respectively, casts at 50 DEG C and form a film for 24 hours.?
At room temperature, by film impregnate in deionized water 12h to remove impurity.Then, film is immersed in 12h in acid, carries out it abundant
Ion exchange.Film is impregnated in deionized water again, removes extra acid.SPEEK/PPO-TA (10%) film, the film is made
Water absorption rate is 38.7%, and surface resistance is 0.364 Ω cm2, and vanadium ion permeability is 0.59 × 10-8cm2s-1, in all-vanadium flow battery
In monocell test, in 80mAcm-2When current density, CE 95.16%, VE 91.88%, EE 87.43%.In 1.5M
VO2 +/3M H2SO4Mass loss after impregnating 45 days in solution is 7.69%.
Embodiment 10
The preparation of trunk polymer SPEEK is with described in example 1, and the preparation of trunk polymer PPO-TA is the same as described in example 9.Point
It does not take 0.105g SPEEK and 0.045g PPO-TA to be dissolved in 4mlDMF, casts at 50 DEG C and form a film for 24 hours.At room temperature, by film
Impregnate in deionized water 12h to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.
Film is impregnated in deionized water again, removes extra acid.SPEEK/PPO-TA (30%) film is made, which is
30.3%, surface resistance is 0.418 Ω cm2, and vanadium ion permeability is 0.79 × 10-8cm2s-1, surveyed in all-vanadium flow battery monocell
In examination, in 80mAcm-2When current density, CE 93.45%, VE 90.62%, EE 84.68%.In 1.5M VO2 +/3M
H2SO4Mass loss after impregnating 45 days in solution is 3.84%.
Embodiment 11
The preparation of trunk polymer SPEEK is with described in example 1, and the preparation of trunk polymer PPO-TA is the same as described in example 9.Point
It does not take 0.075g SPEEK and 0.075g PPO-TA to be dissolved in 4mlDMF, casts at 50 DEG C and form a film for 24 hours.At room temperature, by film
Impregnate in deionized water 12h to remove impurity.Then, film is immersed in 12h in acid, it is made to carry out sufficient ion exchange.
Film is impregnated in deionized water again, removes extra acid.SPEEK/PPO-TA (50%) film is made, which is
28.6%, surface resistance is 0.462 Ω cm2, and vanadium ion permeability is 0.51 × 10-8cm2s-1, surveyed in all-vanadium flow battery monocell
In examination, in 80mAcm-2When current density, CE 96.18%, VE 90.11%, EE 86.67%.In 1.5M VO2 +/3M
H2SO4Mass loss after impregnating 45 days in solution is 3.46%.
Claims (6)
1. a kind of tertiary amine groups amphoteric ion exchange membrane, which is characterized in that the tertiary amine groups amphoteric ion exchange membrane is tertiary-aminated
Polyphenylene oxide and sulfonated polyether-ether-ketone polymer, structure are：
Tertiary amine group contained in tertiary amine groups amphoteric ion exchange membrane has the ability for receiving proton, as proton acceptor；Proton
Receptor forms " acid-base pair " structure with the sulfonic acid group as proton donor, and " acid-base pair " structure is connected by hydrogen bond, has effective
Resistance vanadium and promote proton conduction ability.
2. a kind of preparation method of tertiary amine groups amphoteric ion exchange membrane, which is characterized in that synthetic route is as follows：
Specific step is as follows：
(1) under the conditions of ice-water bath, polyether-ether-ketone is dissolved in the concentrated sulfuric acid, is vigorously stirred；After polymer is completely dissolved,
Reaction temperature is increased to 40 DEG C -80 DEG C, reaction a period of time；To after the reaction was completed, reaction solution be poured into the ice water of stirring
In, it is sulfonated polyether-ether-ketone polymer that precipitating, which is precipitated,；The product is cleaned repeatedly with deionized water, until pH value reaches neutral,
Then it is completely dried under vacuum conditions；
(2) under stirring, PPO is dissolved in methylene chloride, PPO solution is made；Under nitrogen protection, into methylene chloride
Aluminum trichloride (anhydrous) is added and is vigorously stirred, under the conditions of ice-water bath, is slowly added to certain proportion 4- fluorobenzoyl chloride, is mixed
Close solution；PPO solution is then added in mixed solution, 8h or more is reacted at 50 DEG C -80 DEG C；After the reaction was completed, it will react
Liquid pours into a large amount of ethyl alcohol, and it is to be acylated PPO polymer that precipitating, which is precipitated,；Polymer is washed repeatedly with water and ethyl alcohol, vacuum
Drying；
(3) the acylation PPO polymer for taking step (2) to synthesize is dissolved in dimethyl acetamide (DMAC), and certain ratio is then added
2,4,6- tri- (dimethylamino methyl) phenol and excessive cesium carbonate of example react 8h or more at 80 DEG C -120 DEG C；It is reacting
In the process, nitrogen is bubbled in the solution, in favor of the removal of water；After reaction, reaction solution is poured into a large amount of methanol, is precipitated
Obtain tertiary amino functional PPO finally；Then water and the thorough wash products of methanol are used, are dried in vacuo；
(4) PPO-TA of the SPEEK that (1) synthesizes the step of different proportion and step (2) synthesis is taken to be dissolved in casting film agent respectively, at
Concentration is the casting solution of 20g/L-50g/L；Casting solution is added dropwise on casting film glass plate, and sufficiently drying in an oven, is made
With a thickness of 30 μm -70 μm of tertiary amine groups amphoteric ion exchange membrane；A small amount of water is added in tertiary amine groups amphoteric ion exchange membrane, and will
It is gently removed from casting film glass plate；At room temperature, prepared tertiary amine groups amphoteric ion exchange membrane is immersed in deionized water
Middle 12h is to remove impurity；Then, it is immersed in 12h in acid, it is made to carry out sufficient ion exchange；It is impregnated again later
In deionized water, extra acid is removed.
3. preparation method according to claim 2, which is characterized in that the casting film agent is dimethylformamide, diformazan
Yl acetamide, dimethyl sulfoxide, N methyl pyrrolidone be one of or two or more mixed solvents, dry film temperature be 40 DEG C-
70 DEG C, the baking film time is 15h-36h.
4. preparation method according to claim 2 or 3, which is characterized in that the acylation PPO synthesized in step (2) and (3)
With the degree of substitution of tertiary amino functional PPO according to the 4- fluorobenzoyl chloride and 2 being added, 4,6- tri- (dimethylamino methyl) phenol with
Depending on the ratio of PPO, up to 100%.
5. preparation method according to claim 2 or 3, which is characterized in that according to SPEEK and PPO-TA ratio in step (4)
The example different amphoteric ion exchange membrane SPEEK/PPO-TA (X%) that different mixture ratio is made, X are quality shared by PPO-TA in film
Than up to 100%.
6. the preparation method according to claim 4, which is characterized in that in step (4) not according to SPEEK and PPO-TA ratio
It is mass ratio shared by PPO-TA in film with the amphoteric ion exchange membrane SPEEK/PPO-TA (X%) that different mixture ratio is made, X, most
A height of 100%.
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| CN114824393B (en) * | 2021-01-29 | 2024-01-30 | 武汉氢阳能源有限公司 | Quaternary amine salt composite proton exchange membrane and preparation method thereof |
| CN113363542A (en) * | 2021-06-09 | 2021-09-07 | 深圳市通用氢能科技有限公司 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN114405286A (en) * | 2021-12-08 | 2022-04-29 | 华东理工大学 | Ion-crosslinked amphoteric ion exchange membrane, preparation method and application thereof in selective electrodialysis |
| CN114405286B (en) * | 2021-12-08 | 2024-06-28 | 华东理工大学 | Ion crosslinking type amphoteric ion exchange membrane, preparation method and application thereof in selective electrodialysis |
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